Ferromagnetic materials

ABSTRACT

PCT No. PCT/GB91/00346 Sec. 371 Date Oct. 19, 1992 Sec. 102(e) Date Oct. 19, 1992 PCT Filed Mar. 5, 1991 PCT Pub. No. WO91/14271 PCT Pub. Date Sep. 19, 1991.This invention provides a ferromagnetic material Fe60MxNy where M is at least one element selected from Al, Ga, In and Tl, N is at least one element selected from P, As, Sb and Bi, x has a range of 1&lt;/=x&lt;/=39 and x+y=40 and excluding Fe60GaXASy. A preferred ferromagnetic material is Fe60GaxAsy , preferably when x has a range of 3&lt;/=x&lt;/=37, more preferably when x has a range of 20&lt;/=x&lt;/=37, and even more preferably when x has a range of 30&lt;/=x&lt;/=37. Typically, ferromagnetic materials of this type can be homogenised by annealing or melt spinning. Melt spun Fe60GaxAsy can show Curie Temperatures (Tc) of about 470 DEG  C. and saturation magnestions of about 89 emu/g. Typically a ferromagentic material of the Fe60MxNy has a B82 type structure.

SUMMARY OF THE INVENTION

This invention relates to ferromagnetic materials.

Ferromagnetic materials display a marked increase in magnetisation in an independently established magnetic field. The temperature at which ferromagnetism changes to paramagnetism is defined as one Curie Temperature, T_(c).

Ferromagnetic materials may be used for a wide variety of applications such as motors, electromechanical transducers. Most of these applications use ferromagnets made from SmCo₅, (K Strnat et. al. J App Phys 38 p1OO1 1967), Sm₂ Co₁₇, (W Ervens Goldschmidt Inform 2:17 NR, 48 P3 1979), Nd₂ Fe₁₄ B (M Sagawa et. al. J App Phys 55 p2083 1984) and AlNiCo or ferrites (B D Cullity, Introduction to Magnetic Materials, Addison Wesley Publishing).

Nd₂ Fe₁₄ B has one of the highest reported Curie Temperatures of rare earth-iron based alloys at 315° C. The inclusion of iron within an alloy is a well-established method of producing a ferromagnetic material. Iron has been used to dope GaAs in order to produce a material with ferromagnetic properties. I R Harris et. al. (J Crystal Growth 82 p450 1987) reported the growth of Fe₃ GaAs with a T_(c) of about 100° C. More recently (International Patent Application Number PCT/GB 89/00381) it has been shown to be possible to obtain Curie Temperatures higher than those of Nd₂ Fe₁₄ B with M₃ Ga_(2-x) As_(x) where 0.15≦×≦0.99 and M may represent Fe is partially substituted by either manganese or cobalt. Where M=Fe, and x=0.15 then the material is characterised by Curie Temperature of about 310° C. Other ferromagnetic materials include that of GB 932,678, where the material has a tetragonal crystal structure and a transition metal composition component range of 61 to 75 %, and an amorphous alloy ferromagnetic filter of the general formula M_(x) N_(y) T_(z) where M is selected as at least one element from iron, nickel and cobalt, N is at least one metalloid element selected from phosphorous, boron. Carbon and silicon and T is at least one additional metal selected from molybdenum, chromium, tungsten, tantalum, niobium, vanadium, copper, manganese. zinc, antimony, tin, germanium, indium, zirconium and aluminum and x has a range of between 60 and 95%.

According to this invention a ferromagnetic material having a B8₂ type crystal structure comprises Fe₆₀ M_(x) N_(y) where M is at least one element from the group of Al, Ga, In and Tl, N is at least one element from the group of P, As, Sb and Bi, where 1≦×≦39 and where x+y =40 and excluding Fe₆₀ Ga_(x) As_(y). .

Preferably the ferromagnetic has a composition where M is gallium and N is antimony. This preferred material preferably has a preferred range of x of 3≦×≦37, and even more preferred range of 20≦×≦37 and most preferably a range of 30≦×≦37.

The ferromagnetic material can be produced by methods including casting, which may be carried out in a Czochralski growth furnace. Where constituents of the ferromagnetic material are volatile at the high temperatures required for production, such as eg P and As, then an encapsulation layer is used to stop loss of the volatile constituents. A typical encapsulant is B₂ 0₃.

Where homogenisation of the phases within the material is required, then techniques such as annealing or melt spinning may be employed. A typical annealing program is one carried out at a temperature between 600° C. and 900° C. for a time length of between 7 and 21 days.

BRIEF DESCRIPTION OF THE DRAWINGS

This invention will now be described by way of example only, with reference to the accompanying diagram: FIG. 1 is a schematic representation of a casting furnace.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Production of the ferromagnetic material by casting techniques may be seen in FIG. 1. A pyrolitic boron nitride (PBN) crucible 1 is placed within a furnace 2. The PBN crucible contains melt constituents 3 in appropriate ratios and typical purity values of 99.999%. With the PBN crucible in the furnace, valves 4 and 5 are closed, valves 6 and 7 are opened, And vacuum pump 8 pumps the furnace down to a vacuum of about 10⁻³ Torr. When a vacuum of this level is achieved, valves 6 and 7 are closed, the vacuum pump is stopped and valves 4 and 5 are opened. With valves 4 and 5 open, a continuous flow of high purity nitrogen gas is flushed through the furnace 2. The furnace is then heated up as quickly as possible until the melt constituents are molten. Boric oxide 9 forms an upper encapsulating layer on melting and prevents loss of volatile melt constituents.

The furnace is maintained at the elevated temperature for about 2 hours in order to facilitate substantially a fully homogeneous mixture of melt constituents. The furnace 2 is then switched off, with the PBN comacible 1 and its contents brought down to ambient temperature by .Furnace cooling in a flowing nitrogen atmosphere.

Where homogenisation of the ferromagnetic material is required the production may include an annealing process. A typical annealing program is to elevate, and maintain, the as cast material to temperature of about 800° C. for about 14 days in a vacuum of about 10⁶ Torr. followed by furnace cooling.

Table 1 gives, by way of example only, specific compositions where M is gallium and N is antimony with typical saturation magnetization and T_(c) values. It can be seen that for some compositions these values are provided for annealed samples, whilst all samples have typical melt spun values. Table 2 gives typical X-Ray diffraction data concerning lattice constants of ferromagnetic material where M is gallium and N is antimony

                  TABLE 1                                                          ______________________________________                                                T.sub.c (°C.)                                                                             M.sub.s (emu/g)                                       Ga/Sb    Annealed M Spun     Annealed                                                                              M Spun                                     ______________________________________                                         10/30     83      128        36     41                                         20/20    309      308        72     68                                         22.5/17.5                                                                               377      362        79     76                                         25/15             382        81     78.5                                       27.5/12.5                                                                               431      384        83     81.5                                       29/11             389               84                                         30/10             431        88     82                                         32/8     461      360        94     82                                         33/7              470               85                                         34/6     472      463               89                                         36/4              458                                                          38/2              458               89                                         ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                         Atomic % Annealed        Melt Spun                                                                          at vol            at vol                          Fe  Ga     Sb    a (Å)                                                                            c (Å)                                                                            (Å.sup.3)                                                                        a (Å)                                                                            c (Å)                                                                            (Å.sup.3)                   ______________________________________                                         60  10     30    4.111 5.141 15.05 4.127 5.147 15.19                           60  20     20    4.108 5.110 14.94 4.110 5.116 14.97                           60  25     15    4.108 5.085 14.86 4.107 5.108 14.88                           60  30     10    4.105 5.066 14.79 4.106 5.074 14.82                           60  32      8    4.104 5.067 14.78 4.108 5.063 14.80                           60  34      6                      4.103 5.051 14.73                           60  36      4                      4.106 5.043 14.73                           60  38      2                      4.114 5.030 14.75                           ______________________________________                                     

We claim:
 1. A ferromagnetic material having a B8₂ crystal structure consisting essentially of Fe₆₀ M_(x) N_(y) where M is at least one element selected from the group consisting of Al, Ga, In and Tl; N is at least one element selected from the group consisting of As, Sb and Bi; where x has a range of 1≦×≦39; and where x+y=40 and wherein when M is Ga, N is not As.
 2. The ferromagnetic material according to claim 2 where M is Ga and N is Sb.
 3. The ferromagnetic material according to claim 2 where x has a range of 3≦×≦37.
 4. The ferromagnetic material according to claim 3 where x has a range of 20≦×≦37.
 5. The ferromagnetic material according to claim 3 where x has a range of 20≦×≦37 .
 6. The ferromagnetic material according to claim 4 where the material has been homogenized.
 7. The ferromagnetic material according to claim 6 where homogenization has been achieved by annealing.
 8. The ferromagnetic material according to claim 7 where annealing has been carried at a temperature of between 600° C. and 900° C.
 9. The ferromagnetic material according to claim 6 where homogenization has been achieved by melt spinning.
 10. A ferromagnetic material having a B8₂ crystal structure consisting essentially of Fe₆₀ M_(x) N_(y) where M is at least one element selected from the group consisting of Al, Ga, In and Tl; N is at least one element selected from the group consisting of As, Sb and Bi; where x has a range of 30≦×≦39; and where x+y=40 and wherein when M is Ga, N is not As. 